Increasing platinum catalyst activity



Aug. 11, 1959 Filed Deo'. 27, 1954 M. J. DEN HERDER l INCREASING PLATINUM CATALYST ACTIVITY FOR` HYDROFORMING HYDROFINED NAPHTHA 2 Sheets-Sheet 1 Marv/n Den Herder INVENTOR.

ATTORNEY Aug. 1l, 1959 M; J. DEN HERDER 2,899,378

A INCREASING PLATINUM cATALYsT ACTIVITY FOR HYDROFORMING HYDROFINED NFHTHv Marvi/1l J. Den Herder IN VEN TOR.

INCREASING PLATINUM CATALYST ACTIVITY FR HYDROFORMING HYDROFINED NAPHTHA Deli Herder, Chicago, y11.1-, assignor .to ,Standard vffOil'lorflpmly, Chicago, 111-3' .a corporation@ ,Indiana :Application December 27, 1954, Serial No.477,715

v 3 Claims. (Cl. 208-365) `This invention relates to improving platinum catalyst activity for hyd-roforming a naphtha charge which has previously been hydroiined for effecting substantial desulfurization and it pertains'more particularly to an irnprovement in the Ultraforming process (The Petroleum Engineer, volume XXX/l, April 1954, page 3-36).

-I-t has previously been proposed to desulfurize a naphtha charging stock prior to hyd-reforming with/platinum catalysts rbecause large amounts of sulfur have been lfound to be deleterious to platinum catalyst activity -under hydroforming conditions. While hydroli-ning is effective f or removing most of the sulfur and nitrogen from naphthas, it has been found that with many charging stocks hydrolining removes desirable components of an initial naphtha charge :and/orconverts original components into other forms with the net result that the hydroiined charge causes adilferent type of platinum catalyst deactivation in the subsequent hydroforming step. An object of this invention is to pro'videa method and means for preventing ori minimizingthe increased rate of deactivation of platinum catalyst which is caused by the lnaphtha charging stock thereto having been initially h-ydrofined.Y )hter objectsj will beapparent as the detailed description of the rinvention proceeds'.

In practicing the invention a sulfurand/or olen-containing. naphtha charge is hydroiined with any known, hyd-roning or'hydrodesulfurization catalyst under condi-- tions to substantially eliminate its sulfur content and -'to produce a saturated hydroned naphtha having otherwise substantially the same boiling range and composition as the original charge. Since lthe hydroiining necessarily removes at least a`portion of the 4halide. (usually chloride) content of the original raw charge, I add back 'to Ithe hydroiined naphtha about 0.1 tov l0, ybut less Ithan 40, parts per million of a halogen in the -form of a `halogen or halogen-.affording substance before contacting the hydro fined naphtha with platinum-onaluminav catalyst under hydroforming conditions. The halogen-atiording vsubstance may be 'a halogen itself, such as chlorine or bromine, or it may be a halide acid such as HC1, HF or HB1', or it maybe an alkyl halide such as 4tertiary butyl chloride.

A'The halide is preferably added to the hydroned charge only in catalyst-promoter quantities since larger amounts f halide, Le. upwards of about 40 parts per million, cause excessive hydrocracking which it is desired to minimize. Most virgin naphthas naturally contain about 0.1 to l0" parts. per million of halide and this amount of promoter halideis usually adequate for catalyst promoting effect Whenthe yvirgin naphtha is of suliciently low sulfur conthe original charge, as well as removing sulfur and nitro- Patented Aug. l1.1, 195.9

gen therefrom, and removes or alters other components of the charge so that a diierent type of catalyst deactivation is encountered. The addition of sufficient halide to compensate for halide lost in the hydrofining step causes a decrease in the catalyst activity decline rate; this better activity maintenance is obtained without substantially increasing the amount of carbon formation over vthat which f would be obtained by hydroforming -with platinum-on-l alumina catalyst a hydrofned naphtha to which no halide has been added back. v The invention is particularly applicable to an Ultraforming process which operates at relatively low pressures of aboutY 100 to 350 p. s.i. and high inlet temperatures of the order of 900 to 9 509 F. whereby hydrocracking of parans is minimized and the conversion of parains to, aromatics by dehydrocyclization is maximized, the Ultraforming process being regenerative. The additionf of y-halide win promoter amounts to the hydroiined Ultra former charge is preferably substantially constant through` out each on-stream period and, the halide promoter may be separately introduced `into each reactor since the purpose ofthe promoter is to increase overall catalyst activity and the amounts employed are too small vto have any appreciable effect o n cracking and carbon formation.

The invention will be more clearly understood :from

the Afollowing detailed description of a preferred example read in conjunction with vthe accompanying drawings i which form a part of the specilication and in which:

AFigure l is a schematic flow diagram of the improved hydroning-Ultraforming system incorporating the addi.-v

tion o f halide promoter to hydroiined charge, and

Figure 2 is a graph illustrating the Vpromotional eiiect of added halide on platinum catalyst activity (as indicated by product octane number) when employed in `a hydro..

ned naphtha. K .l

lll/hilo the invention is applicable to charging stocks from any crude source, it will be described as applied tof the conversion of a Mid-Continent naphtha having an vend point of about 360 F., a CFR-R octane number kof about 45, a sulfur content of about .03 percent and a kchloride con-tent of about 5 p.p.m. (parts per million), such stock usually consisting of about 50 volume percent parafnsg;` 42 volume percent lnaphthenes and 8 volume percent aromatics. The corresponding Gulf Coast naphtha would be richer in naphthenes and aromatics and containless.

para-funs while an Arkansas naphtha would be richer in paraiiins but would contain less lnaphthenes yand aromatics. vl and also somewhat less chloride, i.e. about I2 parts perA mill-ion. While the invention is described as applied uto naphthas, xit will be understood that it is also ap.- plicable to naphthas from catalytic cracking, thermal cracking, coking and the like, either alone or -in admini ture with virgin naphthas.

The Mid-Continent naphtha charge is introduced from source 10 through line 1 1 to preheater `12 along with about 600 to 1500 cubic feet kof hydrogen-rich gas per barrelof charge from line :13. The naphtha and hydrogen-rich gas are heated to a temperature in the range of about 600 to 800,.e.g. 750 F., under a pressure in the range of aboutto Y1500 p.s.i., eg. about 300 p.s.i., and introduced by' transfer lineV 14 into hydrofining reactor .i15 wherein -it is contacted with a hydroiining catalyst which is preferably4 cobaltoxide-,molybdenum'oxide on alumina. P Iydroiii-V ing catalysts may be made by' impregnatin'g lknown fective for reducing the sulfur content of the charge to the desired low level; platinum-on-alumina catalysts have been found highly satisfactory for this purpose and, although bauxite and fullers earth may be used in some circumstances, it is preferred to employ catalysts which are more effective for hydroning. The space velocity in the hydrotining or desulfurization zone will depend upon the particular charging stock and catalyst; generally speaking, the space velocity should be of the order of 1 to l liquid volumes of charging stock per hour per volume of catalyst in the reactor. It is preferred that the hydronng be etected under conditions for saturating any olens in the charge and for removal of contaminants, particularly nitrogen compounds and excessive amounts of sulfur. Hydroning at higher pressures is usually more effective than hydroning at lower pressures. The hydrofning step itself is well known to those skilled in the art and requires no further detailed description.

The effluent from the hydroning reactor is introduced by lines 16 and 17 into fractionator 1 8 which is pro-l vided with reboiler 19. As described in co-pending application Serial No. 379,810, tiled September 14, 1953,

now Patent No. 2,800,428, granted July 23, 1957, the heat n in the ellluent stream from the hydroning reactor may be employed in reboiler 19. Fractionator 18 is operated under conditions to remove light hydrocarbons and gases including HZS overhead through line 20 and, if desired, to remove high boiling hydrocarbons through line 21 to control end-point.

- In the specific example the heart cut of the hydroned product which boils in the range'of about 200 to 360 F.

4 traforming conditions. The catalyst should be substantially free from sodium, iron and molybdenum oxides but it may contain small amounts of silica, titania, boria, and the like, and it may contain additional halide, such as uoride, provided the amount thereof is low enough to avoid excessive hydrocracking. Other catalyst preparation methods may be employed and other types of supports may be used but, since no novelty is claimed in the catalyst per se, no further description thereof is necessary.

With an active catalyst the weight space velocity in reactor 28 may be about 4 to 10 pounds of charge per hour per pound of catalyst therein and the endothermic nature of the reaction will result in a temperature drop across the reactor so that the eiuent withdrawn through line 29 may be at a temperature of about 800 to 850 F.

This elluent is reheated in heater 30 to a temperature in the range of 850 to 950 F. and passed through the second reactor 31 which preferably contains the same amount of the same type of catalyst employed in reactor 28. Here again, due to the endothermic nature of the conversion, the reactor etluent withdrawn through line 32 at a temperature in the range of about 825 to 875 F. is passed through reheater 33 and then introduced into reactor 34 with an inlet temperature in the range of about 850 to 950 F., reactor 34 likewise containing the same amount of the same type of catalyst as in reand which has been substantially freed from HZS and water as well as light hydrocarbons, is withdrawn by lines 22 and 23 to preheater 24 of the Ultraformer system. Recycled hydrogen-rich gas is introduced to the Ultraformer charge through line 25 in amounts of about 2,000 to 8,000 cubic feet per barrel, e.g. about 4,000 cubic feet per barrel. Since the hydrofming operation has removed most of the 5 parts per million of chloride originally contained in the naphtha charge, a promotional amount (0.1 to 10 parts per million) of chloride is introduced through line 26 by a rotameter or other known l measuring and/or injection means. As above stated, the halide may be in the form of a halogen, halide acid or an alkyl halide. The halide should be introduced only in promotional amounts since larger amounts cause excessive hydrocracking and coke formation which is undesirable. As hereinabove pointed out, the halide promoter may be separately introduced into each reactor, i.e. may be introduced by line 26' to the eluent stream in line 29 and by line 26" to the effluent stream in line 32 as illustrated in the drawing.

The hydroned charge, hydrogen and halide promoter, are heated in preheater 24 to a temperature in the range of about 850 to 950 F. and introduced by line 27 to the rst Ultraformer reactor 28 which is operated under a pressure of about 150-400 p.s.i., eg. about 300 p.s.i. The catalyst in reactor 28 is of the platinum-on-alumina type and it may contain about .1 to 2 percent or vmore of platinum although, for practical purposes, approximately .5 weight percent is preferred. The catalyst may be prepared by contacting an aqueous solution of chloroplatinic acid containing about 3.5 grams of platinum per liter with an ammonium sulfide to obtain a stable aqueous solution which is then combined with alumina sol prepared as taught in U.S. Re. 22,196, the resulting mixture then being dried and calcined (note U.S. 2,659,701). Alternatively, the catalyst may be prepared as taught, by Komarewsky in Oil and Gas Journal, June 24, 1943, page 90 et seq. In such methods of catalyst preparation, the nal catalyst contains at least a part of the chlorine introduced with the chloroplatinic acid, but, when only .5 percent platinum is incorporated in the catalyst, the amount `of chloride `introduced Willnot be sucient to actors 28 and 31. For some charging stocks additional reheater-reactor stages may be desirable. The final reactor eluentis withdrawn through line 35 and cooler 36 to separator 37 which may be operated at about 100 F. for separating hydrogen-rich gas from liquid product. The liquid product is then withdrawn through line 38 to a stabilizer; if the initial charge has an end point substantially greater than about 360 F., it may also be desirable to fractionate the nal liquid product to remove 1 heavy ends therefrom.

v Most of the separated hydrogen-rich gas is recycled by line 25 for introduction into line 23 as hereinabove described. The net amount of produced hydrogen is introduced by line 39 to absorber 40 wherein itis scrubbed z with heavy naphtha introduced from line 21 through line 41 and cooler 42 for recovering condensable hydrocarbons. The rich absorber oil is returned by line 43 and line 17 to fractionator 18. The net production of heavy hydrocarbons is withdrawn through line 44. The hydrogen-rich gas from the top of absorber 40 is introduced by line-13 to line 11 as hereinabove described in order to supply the hydrogen required for the hydrolining step, any additional hydrogen being Iwithdrawn from the system by line 45.

. The Ultraforming system is described in more detail in U.S. 2,773,014, and the combination of hydroning with hydroforming is described in more detail in U.S. 2,800,- 428. In the Ultraforming system a swing reactor" (not shown) is usually employed so that it may be substituted f ,for any one of reactors 28, 31 and 34 when the latter require regeneration and/or rejuvenation. Connections 46, 46 and 46" and 47,'47' and 47" are for the purpose of supplying purge gas, regeneration gas, rejuvenation gas, hydrogen and stripping gas to reactors 28, 31

if. and 34, respectively, in order to provide for regeneration and rejuvenation. With a regenerative hydroforming system such as Ultraforming, catalyst activity may be restored in each reactor from time to time so that there 1s no serious detriment to a slight decline in catalyst activity during each oli-'stream period. For example,

when it isdesired to produce a 92 octane number product, than 92 octane number and, after 100 hours or so, the product may be somewhat lower than 92 octane number, but it is desirable that the total on-stream period be several hundred hours before the product pool falls below the 92 octane limit at which time regeneration and re` juvenation is employed.

result inexcessive amountsbf hydrocracking .underiUl- To demonstrate the results obtainable andsho'w the aseaavs eitect of adding back limited amounts of chloride to a hydroned charging stock:

Run A was made by hydroforming a raw Mid-Continent naphtha -over platinum-onalumina catalyst at 900 F and 27S `psig.,Y with a space velocity of 2 volumes of oil per hour per volume of catalyst, and with 5000 cubic feet of recycled hydrogen perbarrel ofA stock charged, with no scrubbing of recycled hydrogen. v

- `un B wasfmade under substantially` the same conditions as Run A on the naphtha charge after it had been hydrofned over platinum-on-alumina catalyst to effect desulfurization, inspections of the raw naphtha and` hydrotned naphtha being approximately as follows:

Run C was made under the conditions of run A on the hydroned charge with about 6 p.p.m. of chlorine added back.

Run D was made under the conditions of run A on the hydrolined charge with about 40 p.p.m. of chlorine added back.

In each run, the C+ fraction of the product was tested for CFR-R octane number from time to time during the course of the run and the data thus obtained were plotted to show the rate of catalyst activity decline as measured by said octane numbers. The plotted data are shown in Figure 2, from which it will be noted that the activity decline rate for the hydroned charge (run B) was much more rapid than for the raw charge. By adding back to the hydrofined charge (run C) the 6 p.p.m. of chlorine, the activity decline rate was substantially the same as that of raw charge (run A), By adding back 40 p.p.m. of chlorine the activity decline rate was still substantially the `saine as that of the raw charge, but the activity level was higher. The difference in the slope of curve B from that of curves A, C and D shows that by adding back chlorine to hydrofined naphtha charge the unduly rapid rate of catalyst activity decline can be substantially avoided.

While the 40 p.p.m. of chlorine addition increased the overall activity of the catalyst, it also increased the rate of cracking and of carbon formation as is shown by the following data:

Hours on Coke on Chloride Percent stream cat., on cat., coke/100 weight weight hrs. percent percent 560 2. 3 48' 4l 400 6. 2 O65 1. 55 280 4. 2 67 l. 49 520 9. 5 1. 06 l. 82

6. with hydrofined naphtha. lThe addition of 6 p.p.m. of chloride to hydroned charge in this case showed even less coke formation than 'was obtained with the hydroned charge, and Vit did not cause anappreciable inf crease in the chloride content of the catalyst, `which likewise appears to be desirable because excessive amounts ing"v and coke deposition.

moters (U.S. 2,213,345), reforming promoters (U.S. 2,194,186), hydrocracking promoters (U.S. 2,119,647), and hydrogenation promoters (Jour. Am. Chem. Soc. 58, September 1936, p. 1594 et seq.), it was not heretofore appreciated that Virgin naphthas contained sufficient chloride to have a promotional effect in platinum-on-alumina catalyst hydroforming operations, such chloride being lost in a hydroiining operation nor that the use of halide promoters in a hydroned charge would decrease the rate of catalyst deactivation. With the Mid-Continent naphtha tested, the addition of 6 p.p.m. of halide was found to alter the decline rate of the catalyst activity curve and to restore it to the decline rate of unhydroned naphtha. The hydroning operation is desirable in order to prevent the excessive sulfur level in the platinum hydroformer from causing its type of deactivation. By this invention, the detrimental eiect of hydroning is minimized and it is thus possible to obtain greater yields of higher octane number products for longer on-steam operating periods in the Ultraforming process than has heretofore been possible.

I claim:

l. In the process of producing high octane number motor fuel from a low octane number naphtha containing both sulfur and chloride wherein the naphtha is hydroiined under conditions to remove most of said sulfur and chloride, then fractionated to remove water, light hydrocarbons and hydrogen sulfide and then contacted in at least initial, intermediate and final stages with platinum-on-alumina catalyst under hydroforming conditions, the method of eliminating the type of catalyst deactivation which would otherwise be caused by said chloride removal without substantially increasing the rate of cracking and carbon formation, which method comprises introducing into the hydroiined naphtha after the fractionation step and prior to the nal hydroforming stage an amount of chloride in the range of about .l to 10 parts per million, adding at least a part of said chloride to the eluent stream from the first hydroforming stage before it enters the last hydroforming stage, contacting `said naphtha with said platinum-on-alumina catalyst in each of said stages under pressures in the range of to 400 p.s.i. at inlet temperatures in the ranges of about 850 to 950 F. until the activity of the catalyst declines in at least one of said stages, and regenerating the catalyst in each `stage when the activity thereof declines below that required for obtaining a product of desired octane number.

2. The method of claim 1 which includes the step of adding at least a part of said chloride to the ellluent stream Ifrom the first stage before it enters the intermediate stage.

3. In the process of producing high octane number motor fuel from a low octane number, sulfur-containing naphtha wherein the naphtha is hydroined under conditions to remove most of said sulfur and most of any chloride which said naphtha may contain, wherein water, light hydrocarbons and hydrogen sulde are removed from the hydroiined naphtha and wherein said hydroiined naphtha is thereafter contacted in at least initial, intermediate and rlinal stages with platinum-on-alumina catalyst under hydroforming conditions, the improved method of operation which comprises introducing into the hydroflned naphtha after the removal of hydrogen sulfide therefrom and prior to the iinal hydroforming stage an amount of chloride in the range of about .1 to 10 parts Althoughit is known that nalides are cracking pro`vv per million, adding at least a part `of said chloride 'to product having a desired octane number without suffering Y aV yield loss due to hydrocracking and regenerating the catalyst in the respective hydroforming stages when there has been a decline in the activity of the catalyst therein.

e l References Cited in the file of this patent i" 1 .A vUNIIEDsTATEsPATENTs; y s .Y f

v Hartley Oct. 12, 1954 UNITED STATES PATENT OFFICE CERTiFCATE 0F CRRECTION Patent No., 2,899,137@ August ll, 1959 Mervin J o Den Eerdere It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Golimm 4, line' 68, after "product," insert nthe initial onnstream operation may give e product b ighei Signed and sealed this lst day oi Marold 1960 (SEAL) Attest:

KARL HQ AXLINE ROBERT C. WATSON Commissioner of Patents Attesting fcer 

1. IN THE PROCESS OF PRODUCING HIGH OCTANE NUMBER MOTOR FUEL FROM A LOW OCTANE NUMBER NAPHTHA CONTAINING BOTH SULFUR AND CHLORIDE WHEREIN THE NAPHTHA IS HYDROFINED UNDER CONDITIONS TO REMOVE MOST OF SAID SULFUR AND CHLORIDE, THEN FRACTIONED TO REMOVE WATER, LIGHT HYDROCARBONS AND HYDROGEN SULFIDE AND THEN CONTACTED IN AT LEAST INITIAL, INTERMEDIATE AND FINAL STAGES WITH PLATINUM-ON-ALUMINA CATALYST UNDER HYDROFORMING CONDITIONS, THE METHOD OF ELIMINATING THE TYPE OF CATALYST DEACTIVATION WHICH WOULD OTHERWISE BE CAUSED BY SAID CHLORIDE REMOVAL WITHOUT SUBSTANTIALLY INCREASING THE RATE OF CRACKING AND CARBON FORMATION, WHICH METHOD COMPRISES INTRODUCING INTO THE HYDROFINED NAPHTHA AFTER THE FRACTIONATION STEP AND PRIOR TO THE FINAL HYDROFORMING STAGE AN AMOUNT OF CHLORIDE IN THE RANGE OF ABOUT .1 TO 10 PARTS PER MILLION, ADDING AT LEAST A PART OF SAID CHLORIDE TO THE EFFLUENT STREAM FROM THE FIRST HYDROFORMING STAGE BEFORE IT ENTERS THE LAST HYDROFORMING STAGE, CONTACTING SAID NAPHTHA WITH SAID PLATINUM-ON-ALUMINA CATALYST IN EACH OF SAID STAGES UNDER PRESSURES IN THE RANGES OF 150 TO 400 P.S.I. AT INLET TEMPERATURES IN THE RANGES OF ABOUT 850 TO 950*F. UNTIL THE ACTIVITY OF THE CATALYST DECLINES IN AT LEAST ONE OF SAID STAGES, AND REGENERATING THE CATALYST IN EACH STAGE WHEN THE ACTIVITY THEREOF DECLINES BELOW THAT REQUIRED FOR OBTAINING A PRODUCT OF DESIRED OCTANE NUMBER. 